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US2889315A - Water soluble dye salts and process for the production thereof - Google Patents

Water soluble dye salts and process for the production thereof Download PDF

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Publication number
US2889315A
US2889315A US552294A US55229455A US2889315A US 2889315 A US2889315 A US 2889315A US 552294 A US552294 A US 552294A US 55229455 A US55229455 A US 55229455A US 2889315 A US2889315 A US 2889315A
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parts
acid
amino
blue
solution
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US552294A
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Inventor
Bossard Werner
Voltz Jacques
Favre Francois
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Novartis AG
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JR Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/10—Azo dyes containing onium groups containing cyclammonium groups attached to an azo group by a carbon atom of the ring system
    • C09B44/20—Thiazoles or hydrogenated thiazoles

Definitions

  • the invention concerns water soluble dye salts containing an azo dyestufl as cation and processes for the production thereof from azo dyestufis which contain a benzthiazole ring and which are insoluble in water.
  • R represents preferably a substituent with a positive It can also represent methyl, ethyl, isopropyl, tert. butyl, tert. amyl, 0 methoxy, ethoxy, phenoxy, benzyloxy groups in addition to methyl mercapto or phenylmercapto groups as well as groups forming a ring with a neighbouring substituent such as the dihydroxymethylene group, tetramethylene group or the dioxine ring.
  • Valuable greenish-blue dyestuffs are also obtained if a neighbouring pair of R to R represent a fused benzene ring.
  • the benzene ring of the benzthiazole radical can be substituted within the bounds of the definition as desired, e. g., by halogen, nitro, acylamino, alkyl sulphonyl, carboxylic acid ester, sulphonic acid amide, phenyl or benzyl groups.
  • the p-phenylene radical bound to the azo group can form part of a fused ring system.
  • Either the pair of substituents R and R or the pair R and R can be bound to form rings in such a manner that 5 they can represent either a fused benzene ring or a hydrogenated isocyclic or heterocyclic ring.
  • R to R represent two hydrogen atoms'in the pposition to each. other, as p-aminobenzene azo dyestuffs atent are particularly valuable.
  • R is a substituent usual in azo dyestuffs, e. g. 'an alkyl, alkoxy, acylamino group or a halogen atom. However, it can represent a more negative group such as e.g.
  • R is an alkyl or an alkoxy group
  • the amino group in the p-position can be primary, otherwise it is substituted, preferably organically, i.e. it is either a secondary or advantageously a tertiary amino group.
  • Organic substitutents of the amino group can be aliphatic, araliphatic, cycloaliphatic or aromatic, the heterocyclic-aliph atic groups like the furyl methyl group also being understood by the term araliphatic.
  • the organic substituents can be further substituted, such as for example in the oxalkyl, fluoralkyl, cyanalkyl, alkoxyalkyl, phenoxyalkyl, the alkylbenzyl, halogen benzyl, alkoxybenzyl, alkylphenyl or alkoxyphenyl groups.
  • Aliphatic substituents of the amino group can also form hetero rings among themselves, possibly in cluding ether atonrs or linked to the substituents R and R such as in the piperidino, morpholino, the 1.2.3.4- tetra'hydroquinoline, the lilolidine, the julolidine or the perimidine compounds.
  • One of the two nitrogen substituents is advantageously a cyanethyl, benzyl, or phenyl radical.
  • acid dissociating salt forming groups such as for example the carboxyl and the sulphonic acid group are excluded as substituents.
  • Alkylating agents suitable for the production of the dye salts according to the present invention are the esters of strong mineral acids and organic sulphonic acids of preferably lower alcohols.
  • Alkyl chlorides, alkyl bromides, alkyl iodides, aralkyl halides such as benzyl bromide, benzyl halides substituted at the benzene ring by halogen, alkyl or alkoxy groups, dialkyl sulphates and alkyl-p-methyl benzene sulphates are chiefly used.
  • the azo dyestuffs usable according to the present invention are reacted with the suitable alkylating agents advantageously in inert organic solution, the water soluble dye salts separating out.
  • solvents examples include benzene hydrocarbons, halogenobenzenes and nitro benzenes, high boiling aliphatic and alicyclic hydrocarbons as well as stable halogen alkanes such as carbon tetrachloride, tetrachlorethylene. Also an excess of alkylating agent can be used as solvent.
  • the reaction is exothermic. To start the reaction, however, warming is necessary in particular when there is a large amount of diluent. In some favourable cases however, salt formation also occurs in aqueous or alcoholic solution or suspension, the dye salts formed being dissolved and isolated by salting out.
  • the reaction is performed in organic solvents, these can be removed by filtration or, due to the stability of the dye salts according to the present application, they can be removed either by distilling olf, possibly under reduced pressure or by steam distillation.
  • the dye salts according to the present invention can be obtained from organic solution also byextraction with water. It is of advantage to use an excess of alkylating agent, whereby any primary and secondary amino groups can also be subsequently alkylated. However, the formation of the cyclammonium salt is clearly preferred so that under the usual working conditions dyestuifs do not result which are similar to those with a tertiary p-amino group, from analogous dyestuifs with a primary or secondary p-amino group. If necessary, the dye salts according to the present invention can also be modified subsequently, for example, they can be acyla-ted. 7
  • dyestuffs usable according to the present invention are known, others can be produced by methods knownper Se by diazotising Z-aminobenzthiazole comin the p-position to a primary, secondary :or tertiary amino group, or by alkaline condensation of p-nitroso 'aminoaryl compounds with Z-amihobenzthmzole cornattained with the dyestuffs according to the present in- I vention are often distinguished by their fastness to light.
  • R5 dimethoxybenzene in IOOparts of glacial acetic acid is in) added dropwise at 15 to 5 to the diazo solu- In hi rm 11 t r s n alkyl radical, hi tion.
  • 300 parts of water are can be further' substituted, e.g. aurnethyl, ethyl, propyl, added to the coupling mass and the miueralacid rey s y beniyl, p-methylb y i i 1 s action is buffered with lye until Congo red paper is no represent the?
  • the residue is taken up in 250 partsot warm water can be isocyclic, eg. a fused benzenering, a tetramethyland the solution is clarified with a little animal charene group, or. it can be heterocyclic e; g. a methylenecoal.
  • The'dyesalt is precipitated from thefiltered soludioxy ring, a dioxine ring, a triazole, imidazole, pyra tion. with 1.5 parts of zinc chloride and 25 parts of so-.
  • zole ring or with R and R it can also bea piperidino, dium chloride; .Aftcr drawing off under suction and morpholine or tetrahydro-pyridine ring.
  • X represents drying, the dyestuif dissolves in Water with a blueand the uncoloured anion equivalenttothe; coloured cation, in concentrated sulphuricacid with a yellow'coloun; It 45 Chlorine ions'bl'omine'mn, n6 i011.
  • methosulphate dyes silk, leather, mordanted cotton and polyacryloniion ethosulphate ion, bisulphate ion, sulphate ion, bcn- 'trile fibers from'an acetic acid solution in violet shades zenc sulphonate ion, p-toluene .sulphonate ion; it can which have good fastness properties.
  • the dyestufi is obtained by coupling with the sodium salt of methylaruinobenzene-w-su1phonic acid and then saponifying to form the p-amino-monazo dyestuti.
  • the dye salts according to the present invention can be described as basic dyestufis. Particularly in the formof salts of strong inorganic and organic acids they dissolve well in water. Less easily soluble compounds can be dissolved in diluted aqueous mineral acids.
  • the dye salts according to the present invention dye cotton mordanted with tartar emetic and tannin, silk, leather and synthetic polymeric fibres containing nitrogen which are produced from polyacrylonitrile or chiefly from Example 2
  • a solution of 20 parts of 2-amino-(naphtho-1.2:4.5)- thiazole'in20 parts of acetic acid is added to a mixture acrylonitrile, generally in very pure shades.
  • the dpeings which has been cooled to +-l0 of 220 parts of sulphuric 5 acid 60 B6. and 150 parts of water. It is diazotised Within 2 hours at 10 with 13.4 parts of nitrosyl sulphuric acid, corresponding to 6.9 parts of sodium nitrite and, after stirring the reaction mass for half an hour, it is poured into 1500 parts of ice water.
  • a weakly aqueous/rnineral acid solution of 13.3 parts of N-ethyl-N- benzyl-arnino-benzene is added to the clarified diazo solution at -5, the reaction is buflered until it is neutral to Congo red paper and the brown-violet dyestuif which precipitates is drawn off under suction, Washed and dried.
  • N.N-dl-B-oxethylaminebenzene N.N-dibenzy1amino-benzene N -methyl-N -B-oxethyl-arntnobenzene N methyl-N-fi-cyanethylaminobenzene- ....d0 do 2.1 pants diethyl su1phate-- on.
  • zene, 3-N.N-diethylaminobenzene-1-su1phonic acid amide are used or if 2-amino-(naphtho-1'.2:5.4)-thiazole is used as diazo component.
  • Example 3 A diazo solution is produced from 16.4 parts of 2- amino-6-methy1 benzthiazole, 300 parts of 60% acetic acid, 20 parts of concentrated sulphuric acid and 20 parts of nitrosyl sulphuric acid, corresponding to 6.9 parts of sodium nitrite.
  • a congo acid solution of 24.9 parts of l- N-ethyl-N-benzylamino-3-methoxybenzene in the equivalent amount of 2-N-sulphuric acid is added at 15 to 5 to the diazo solution.
  • the dye salts obtained with all the coupling components given in the above table all dissolve in water with a blueviolet and concentrated sulphuric acid with a yellow colour.
  • Example 4 The monoazo dyestufi from 2-amino-6-ethoxy benzthiazole and l-N-ethylamino-3-methylbenzene is produced as described in Example 1.
  • the blue-black dyestufi. so obtained is filtered off after the reaction mass has been cooled. To further purify, the dyestufi is dissolved in 200 parts "o'f'warn'i Water and is precipitated in the cold with 30 parts of'sodium chloride. It dissolves in water with a violet and in concentrated sulphuric acid with a yellowish colour. The dyestuif dyes silk, mordanted cotton, and polyacrylonitrile fibres from an acetic acid bath in violet shades which have good fastness properties. i
  • Dyestuifs with similar properties are obtained if dyestuffs are alkylated which have the corresponding amounts of the monoalkylated anilines given in the following table as coupling components instead of 1-N-e'thyl-amino- 3-methylbenzene and the amounts of substances given in the table are used and the conditions desribed are kept.
  • the dye salts obtained with the coupling components Nos. 1 to 8 inclusive and with No. 10 all dissolve in water with a violet and in concentrated sulphuric acid with a yellow colour. That obtained with coupling component No. 9 dissolves in water with a blue and in concentrated sulphuric acid with a yellow colour.
  • Example 1 The monoazo dyestufi from 2-amino-6-ehlorobenzthiazole and 1-N.N-dimethylaminonaphthalene is produced as described in Example 3. A solution of 3.6 parts of this dyestuff in 200 parts of abs. alcohol is heated under pressure for 2 hours at 120 with 4.4 parts of ethyl bromide. The reaction mixture is evaporated to dryness and the residue is worked up as described in Example 1. The dye salt isxdried in the vacuum at 70. The blueblack dyestufi dissolves in concentrated'sulphuric acid with a yellow and in water with a blue colour. It dyes polyacrylonitrile fibres, mordanted cotton and silk from an acetic acid bath in vivid red-blue shades. Dyeings of the same shade are obtained with the Zincchloride'double salts.
  • alkylated dyestutfs which are produced from the same diazo compound and the following coupling components: l-N- phenylaminonaphthalene, 1-N.N-dimthylamino-Z-methoxynaphthalene or 1.2.3.4 tetrahydro-5.6-benzoquinoline.
  • Example 6 16.4 parts of 2-arnino-4-rnethyl 'benzthiazole in 200 parts of sulphuric acid 60 B. and 150 parts of water are diazotised within 2 hours with 25 parts of nitrosyl sulphuric acid which correspond to 6.9 parts of sodium nitrite.
  • the clear diazo solution is diluted with 1000 parts of ice water and a solution of 18.3 parts of N- methyl diphenylamine in 200 parts of 15% sulphuric acid is slowly added at 0-5. The whole is stirred for 3 hours, then the mineral acid reaction is buffered with saturated sodium acetate. solution until Congo red paper is no longer coloured blue.
  • the red dyestufl which precipitates in crystalline form is filtered oflf, washed with a lot ofwater and dried in the vacuum.
  • the dry dyestuif is converted into the corresponding cyclammonium salt with dimethyl sulphate in boiling chlorobenzene as described in Example 1.
  • the dark blue methylation product dissolves in water with a blue and in concentrated sulphuric acid with a yellow colour. It dyes polyacrylonit'rile fibres, mordanted cotton, silk and leather from an acetic acid bath in vivid blue shades which have good fastness properties.
  • alkylated dyestuffs which have the following 2-amino benzthiazole derivatives as diazo components instead of, 2-amino-4- methyl benzthiazole: 2-arnino-6-ethyl benzthiazole, 2- ainino-G-phenyl benzthiazole, 2-amino-6-chloro benzthiazole, 2-amino-6-carbethoxy benzthiazole, 2-amino-6- methoxy benzthiazole, 2-amino-6-ethoxy benzthiazole, 2- amino-6-methyl sulphonyl benzthiazole, 2-amino-4-chloro benzthiazole, 2-amino-4-ethy1 benzthiazole, 2-amino-6- thiocyano benzthiazole, 2amino-6-cyano benzthiazole, 2-
  • Example 7 V A diazo solution is prepared from 15 parts of Z-aminobenzthiazole, 300 parts of acetic acid, 20 parts of concentrated sulphuric acid and 20 parts of nitrosyl sulphuric acid, corresponding to 6.9 parts of sodium nitrite.
  • a Congo acid solution of 2.2 parts of l-N-ethyl- N-benzylamino-3-bromobenzene in the equivalent amount of Z-N-sulphuric acid is added dropwise at 15 to 5 to the diazo solution. After stirring the coupling mixture for 2 hours, the mineral acid reaction is buttered with concentrated causticsoda lye until Congo red paper is no longer coloured blue.
  • R represents a member selected from the parts of absolute chlorobenzene and 1.9 parts of diclass consisting of lower alkyl and benzyl radicals, and methyl sulphate in 50 parts of chlorobenzene are added wherein of R to R at least one is other than hydrogen, at the boiling temperature of the solvent.
  • the reaction and X represents an anion. solution is boiled for one hour during which time the 5 2.
  • a dyestuff of the formula: cipitates. After cooling the reaction solution, the pre- CHa cipitated dyestuif is filtered off, taken up in 200 parts I I 1 of warm water, the aqueous solution is clarified with a CH5 little charcoal and the dye salt is precipitated with the aid I of 1.5 parts of zinc chloride and parts of sodium 20 C N N O N O1 Znoh chloride in the form of the zinc chloride double salt. GHaO- The yellow-bronzy powder so obtained is dried in the vacuum at 6070. It dissolves in water with a blue and 4. A dyestufi of the formula:
  • a dyestuif of the formula A dyestufi of the formulai' GB (imam 69 R1 N a, R c n. B
  • UNITED STATES PATENTS R to R each represents a member selected from the 2135 293 Renshaw et aL Nov. :1 1938 class consisting of hydrogen, chlorine, bromine, lower 2:441:612 Argyle et a1.

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US552294A 1954-12-15 1955-12-12 Water soluble dye salts and process for the production thereof Expired - Lifetime US2889315A (en)

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CA (1) CA570913A (de)
CH (1) CH331521A (de)
DE (1) DE1050940B (de)
FR (1) FR1145235A (de)
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Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2980666A (en) * 1957-05-29 1961-04-18 Sandoz Ltd Azo dyestuffs of low solubility in water
US3033847A (en) * 1959-11-30 1962-05-08 Du Pont Cationic monoazo dyes for acrylic and polyester fibers
US3105829A (en) * 1958-02-05 1963-10-01 Sandoz Ltd Monoazo dyestuffs of the benzothiazol series
US3107968A (en) * 1961-02-17 1963-10-22 Du Pont Dyeing of acid-modified acrylic and polyester fibers
US3117911A (en) * 1959-04-23 1964-01-14 Oreal Method of dyeing live human hair
US3121710A (en) * 1958-10-02 1964-02-18 Cfmc Quaternized monoazo dyes containing a 6-hydroxy-indazole radical
US3132133A (en) * 1962-02-28 1964-05-05 American Cyanamid Co Blue cationic azo dye
US3160467A (en) * 1960-05-06 1964-12-08 Cfmc New azo dyestuffs and a process for dyeing polyacrylic fibres
US3179486A (en) * 1962-07-30 1965-04-20 American Cyanamid Co Propylene dyeing method
US3314934A (en) * 1963-01-03 1967-04-18 Basf Ag Basic thiazole-azo dyes
US3405118A (en) * 1965-12-21 1968-10-08 Du Pont 4-methoxy-6-nitrobenzothiazolylazo disperse dyes
US3455898A (en) * 1965-06-10 1969-07-15 Basf Ag Water-insoluble monoazo dyes containing a 2,1-benzoisothiazolyn-(3) radical
US3502645A (en) * 1968-02-16 1970-03-24 Martin Marietta Corp Water-insoluble benzothiazole monoazo dyes
FR2043789A1 (de) * 1969-05-29 1971-02-19 Hoechst Ag
US4041024A (en) * 1970-04-30 1977-08-09 Bayer Aktiengesellschaft Sulfo containing monoazo dyestuffs containing a benzthiazole diazo moiety and an N-benzylamino anilino coupling component
US4251440A (en) * 1974-05-04 1981-02-17 Sandoz Ltd. Monoazo compounds having a thiazolium or substituted thiazolium diazo component radical and a 1,4-phenylene coupling component radical having a C1-4 alkyl group in each ortho position
US4488992A (en) * 1978-12-25 1984-12-18 Sumitomo Chemical Company, Limited Monoazo dyestuffs derived from benzothiazole
DE2733178C2 (de) * 1977-07-22 1985-04-25 Hoechst Ag, 6230 Frankfurt Verfahren zur Herstellung von Tetrachlorzinksalzen
US4997918A (en) * 1982-08-30 1991-03-05 Ciba-Geigy Corporation Benzthiazolium azo dyes
US5163972A (en) * 1989-12-06 1992-11-17 Ciba-Geigy Corporation Process for the dyeing of polyacrylonitrile materials with cationic benzo-thiazolium azo dye
EP0679691A2 (de) * 1994-04-26 1995-11-02 Ciba-Geigy Ag Kationische oder basische Aminobenzthiazol-Farbstoffe
US20170283618A1 (en) * 2016-04-04 2017-10-05 Capacitor Sciences Incorporated Non-linear dielectric materials and capacitor

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1105540B (de) * 1957-10-24 1961-04-27 Basf Ag Verfahren zur Herstellung von Diazapolymethinfarbstoffen
DE1088631B (de) * 1957-10-24 1960-09-08 Basf Ag Verfahren zur Herstellung von Diazapolymethinfarbstoffen
DE1127015B (de) * 1957-12-04 1962-04-05 Basf Ag Verfahren zur Herstellung von wasserloeslichen basischen Farbstoffen
DE1218634B (de) * 1958-10-02 1966-06-08 Kuhlmann Ets Verfahren zur Herstellung von basischen Azofarbstoffen
DE1135593B (de) * 1958-11-03 1962-08-30 Ici Ltd Verfahren zur Herstellung von wasserunloeslichen Azofarbstoffen
DE1271858B (de) * 1962-02-28 1968-07-04 American Cyanamid Co Verfahren zur Herstellung von kationischen Azofarbstoffen
DE1282814B (de) * 1962-04-04 1968-11-14 Basf Ag Verfahren zur Herstellung von Diazapolymethinfarbstoffen
US3342800A (en) * 1962-06-26 1967-09-19 Kewanee Oil Co Benzothiazole monoazo dyes
DE2221989A1 (de) * 1972-05-05 1973-11-15 Hoechst Ag Basische azofarbstoffe, verfahren zu ihrer herstellung und ihre verwendung
DE2255059A1 (de) * 1972-11-10 1974-05-22 Bayer Ag Basische farbstoffe
JPS5112754B2 (de) 1974-02-25 1976-04-22
GB1502861A (en) 1974-05-24 1978-03-08 Sumitomo Chemical Co Dischargeable black dyeing of acidmodified polyester fibr
DE2623162A1 (de) * 1976-05-22 1977-12-01 Bayer Ag Alkylierung von azofarbstoffen
CN105176133B (zh) * 2014-08-13 2017-12-22 东华大学 一种可交联活性分散染料化合物及其制备和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH136921A (de) * 1927-05-21 1929-12-15 Ig Farbenindustrie Ag Verfahren zur Herstellung eines basischen Azofarbstoffes.
US2135293A (en) * 1936-08-20 1938-11-01 Pyridium Corp Medicinal azo dyes
US2441612A (en) * 1941-07-23 1948-05-18 Celanese Corp Benzthiazole azo dye
FR1049896A (fr) * 1952-01-26 1954-01-04 Cfmc Nouveaux colorants azoïques, leurs procédés de préparation et leurs applications

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH136921A (de) * 1927-05-21 1929-12-15 Ig Farbenindustrie Ag Verfahren zur Herstellung eines basischen Azofarbstoffes.
US2135293A (en) * 1936-08-20 1938-11-01 Pyridium Corp Medicinal azo dyes
US2441612A (en) * 1941-07-23 1948-05-18 Celanese Corp Benzthiazole azo dye
FR1049896A (fr) * 1952-01-26 1954-01-04 Cfmc Nouveaux colorants azoïques, leurs procédés de préparation et leurs applications

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2980666A (en) * 1957-05-29 1961-04-18 Sandoz Ltd Azo dyestuffs of low solubility in water
US3105829A (en) * 1958-02-05 1963-10-01 Sandoz Ltd Monoazo dyestuffs of the benzothiazol series
US3121710A (en) * 1958-10-02 1964-02-18 Cfmc Quaternized monoazo dyes containing a 6-hydroxy-indazole radical
US3117911A (en) * 1959-04-23 1964-01-14 Oreal Method of dyeing live human hair
US3033847A (en) * 1959-11-30 1962-05-08 Du Pont Cationic monoazo dyes for acrylic and polyester fibers
US3160467A (en) * 1960-05-06 1964-12-08 Cfmc New azo dyestuffs and a process for dyeing polyacrylic fibres
US3107968A (en) * 1961-02-17 1963-10-22 Du Pont Dyeing of acid-modified acrylic and polyester fibers
US3132133A (en) * 1962-02-28 1964-05-05 American Cyanamid Co Blue cationic azo dye
US3179486A (en) * 1962-07-30 1965-04-20 American Cyanamid Co Propylene dyeing method
US3314934A (en) * 1963-01-03 1967-04-18 Basf Ag Basic thiazole-azo dyes
US3455898A (en) * 1965-06-10 1969-07-15 Basf Ag Water-insoluble monoazo dyes containing a 2,1-benzoisothiazolyn-(3) radical
US3405118A (en) * 1965-12-21 1968-10-08 Du Pont 4-methoxy-6-nitrobenzothiazolylazo disperse dyes
US3502645A (en) * 1968-02-16 1970-03-24 Martin Marietta Corp Water-insoluble benzothiazole monoazo dyes
FR2043789A1 (de) * 1969-05-29 1971-02-19 Hoechst Ag
US4041024A (en) * 1970-04-30 1977-08-09 Bayer Aktiengesellschaft Sulfo containing monoazo dyestuffs containing a benzthiazole diazo moiety and an N-benzylamino anilino coupling component
US4251440A (en) * 1974-05-04 1981-02-17 Sandoz Ltd. Monoazo compounds having a thiazolium or substituted thiazolium diazo component radical and a 1,4-phenylene coupling component radical having a C1-4 alkyl group in each ortho position
DE2733178C2 (de) * 1977-07-22 1985-04-25 Hoechst Ag, 6230 Frankfurt Verfahren zur Herstellung von Tetrachlorzinksalzen
US4488992A (en) * 1978-12-25 1984-12-18 Sumitomo Chemical Company, Limited Monoazo dyestuffs derived from benzothiazole
US4997918A (en) * 1982-08-30 1991-03-05 Ciba-Geigy Corporation Benzthiazolium azo dyes
US5163972A (en) * 1989-12-06 1992-11-17 Ciba-Geigy Corporation Process for the dyeing of polyacrylonitrile materials with cationic benzo-thiazolium azo dye
US5929216A (en) * 1989-12-06 1999-07-27 Ciba Specialty Chemicals Corporation Benzothiazolium containing azo dyes useful for dyeing polyacrylonitrile
EP0679691A2 (de) * 1994-04-26 1995-11-02 Ciba-Geigy Ag Kationische oder basische Aminobenzthiazol-Farbstoffe
EP0679691A3 (de) * 1994-04-26 1996-01-10 Ciba Geigy Ag Kationische oder basische Aminobenzthiazol-Farbstoffe.
US5635607A (en) * 1994-04-26 1997-06-03 Ciba-Geigy Corporation Cationic or basic azo dyes consisting of an amino benzothiazole diazo component and a disubstituted aniline component, which dyes contain at least one aromatic radical
US20170283618A1 (en) * 2016-04-04 2017-10-05 Capacitor Sciences Incorporated Non-linear dielectric materials and capacitor

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IT545975A (de)
GB787369A (en) 1957-12-04
BE543604A (de)
CA570913A (en) 1959-02-17
CH331521A (de) 1958-07-31
FR1145235A (fr) 1957-10-23
DE1050940B (de) 1959-02-19

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